We have been studying the spectral properties of strong coupling states between metallic nanostructures and excitons. We have reported on the modulation and dynamics of the near-field spectral properties of exciton-plasmon strong coupling systems. However, it has been difficult to quantitatively evaluate the phase relaxation times experimentally because the central wavelength of the exciton is far from the central wavelength of the Ti:sapphire laser. Therefore, in this study, we fabricated an exciton-plasmon strong coupling system using an exciton with a central wavelength near 800 nm and aimed to quantitatively clarify the relationship between the near-field spectral characteristics and the phase relaxation dynamics of the system. Peak splitting was observed both in the far-field and near-field spectra, indicating the successful formation of a strong coupling state. We are now trying to measure the phase relaxation dynamics of the strong coupling system.
Transition metal dichalcogenides (TMDs), which are layered compounds, have attracted attention as next-generation semiconductor materials due to their direct bandgap and photoluminescent properties when in monolayer form. In particular, the heterostructures of p-type semiconductor WSe2 and n-type semiconductor MoS2 exhibit Type II band offsets, leading to superior charge separation efficiency, thus offering potential applications in optoelectronic and light-emitting devices. However, their thin layers result in low light absorption efficiency and relatively low photoluminescence quantum yields, posing challenges for device construction utilizing TMD heterostructures. Enhancement of light absorption efficiency and quantum yield improvement can be achieved through electromagnetic field enhancement by localized surface plasmon resonances. This study elucidated carrier dynamics through time-resolved measurements to reveal the details of charge separation induced in TMD heterostructures and to investigate the impact of plasmon resonance on charge recombination rates and photoluminescence intensity.
We have recently found that the interaction between metallic nanostructures exhibiting localized surface plasmon resonance in the mid-infrared wavelength region and molecular vibrational modes significantly reduces the fluorescence and surface-enhanced Raman scattering signals. In addition, in the photochemical reaction of photochromic molecules, a phenomenon in which the reaction is promoted or suppressed has been observed. The purpose of this study is to clarify the phenomenon that the spectroscopic characteristics and reaction characteristics change due to the interaction between plasmons and excited state molecules or molecular vibrational modes through ultrafast spectroscopy.
Plasmon-induced hot electron transfer has attracted much attention as a novel strategy for the solar energy conversions. However, the solar energy conversion efficiency is limited by the insufficient absorption on monolayer of metallic nanoparticles. To solve this problem, in the present study, we apply the principle of strong coupling to plasmonic water splitting induced by the plasmon-excited electron transferring into wide-bandgap semiconductor on a Au nanoparticle (Au-NP)/TiO2 thin-film/Au-film (ATA) photoanode.
Strong coupling between the Fabry-Pérot nanocavity mode of the TiO2 thin-film/Au-film and the localized surface plasmon mode of the Au-NPs is induced when their resonant frequencies overlap. To increase the coupling strength in this strong coupling regime, a key feature is partially inlaying of Au-NPs into the TiO2 nanocavity by several nanometers. Under a three-electrode system measurement with a saturated calomel electrode (SCE) as a reference electrode, a Pt wire as a counter electrode and an electrolyte of KOH (0.1 mol/dm3), we demonstrated that the action spectrum of incident photon to current conversion efficiency (IPCE) exhibited two bands, which almost corresponds to the absorption spectrum of ATA. The IPCE of ATA is extraordinarily enhanced as compared to that of Au-NPs/TiO2 photoanode. Most importantly, under the strong coupling regime, the internal quantum efficiency (IQE) of the photocurrent generation is also enhanced at the strong coupling wavelengths. The increase in IQE implies the possibility of increasing the generation of hot electrons due to the strong coupling. The plasmon-induced water splitting using a two-electrode system is also discussed.
Nanoparticles of noble metals show localized surface plasmon resonance. Plasmon resonances which are collective oscillations of conduction electrons give rise to the enhancement of electromagnetic field to the local surface of metallic nanoparticles. Therefore, various plasmonic near-field lithography systems were proposed so far. Here, we report on a plasmon-assisted nanolithography used for the fabrication of nano-patterns with nanometric accuracy. The lithography system can form deep nano-patterns on positive photoresist film using scattering component of multipole plasmon resonances as an exposure light. Two-photon-induced reaction of a photoresist enabled the formation of fine patterns even using plasmonic scattering light.
Advanced lithography systems, such as ArF immersion lithography, have achieved a 32 nm node1, 2 and are already used
in electronic device development. However, the advanced lithography systems are not suitable for fabricating
nanostructures, such as rectangular cuboids, triangular prisms, chains, and nanogaps. These nanostructures are being
used for various applications that include plasmonic solar cells3-5 and photonic crystal lasers.6, 7 In this proceeding, we
report an innovative lithography system appropriate for fabricating such nano-patterns with nanometric accuracy based
on plasmon-assisted photolithography. The key technology is the two-photon photochemical reaction of a photoresist
induced by plasmonic near-field light and propagating light in a photoresist film. This propagating light is a radiation
mode from a higher order of localized surface plasmon resonances scattered by metallic nanostructures. The system does
not induce nano-pattern deformation at the time of mask release. This system presents a simple alternative for producing
nano-patterns instead of using nanoimprinting.
Highly homogeneous arrays of Ag, Au and Cu nanorods were fabricated on glass substrates using electron-beam lithography and lift-off techniques. Optical properties of the fabricated structures related to localized surface plasmons (LSP), and their dependencies on the nanorod size were studied experimentally by optical extinction spectroscopy. Spectral tuning of LSP resonant scattering bands in a wide spectral range, from visible to near-infrared wavelengths, can be accomplished by tailoring of the nanorod dimensions, aspect ratios, and heights. The observed results qualitatively agree with Gans theory and numerical modeling by finite-difference time-domain technique.
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